Phosphonitrilic chloride: 23. Substitution reaction of phosphonitrilic chloride trimer with sodium hydroxymethylphenolate and polymerization of substitution products

Abstract

Chlorine substitution reactions of phosphonitrilic chloride trimer (PNCl 2) 3 with 2-, 3- or 4- HOH 2CC 6H 4ONa and 2-NaOH 2CC 6H 4ONa were carried out in dioxane solvent under various experimental conditions. All reactions were completed in 40–200 min in the temperature range 60° to 100°C. The chemical shifts of P atom were measured by 31P n.m.r. spectroscopy of P 3N 3(2-HOH 2CC 6H 4O) 6 (I), P 3N 3(3-HOH 2CC 6H 4O) 6 (II), P 3N 3(4-HOH 2CC 6H 4O) 6 (III) and P 3N 3(2-OH 2CC 6H 4O) 3 (IV). The 31P n.m.r. spectra showed the singlet peak. Water vapour and formaldehyde were detected by gas chromatography and polymers were formed when (I), (II) and (III) were heated from 150°C to 250°C. The polymers were stable towards water. Further, thermal balance measurements showed that the polymer formed from (I) was the most stable. The resistivity of films formed when (I), (II) and (III) were heated at about 300°C for 2 min was 1–10 × 10 13 Ω- cm . Thermal decomposition occurred rather than ring cleavage reaction when (IV) was heated from 150°C to 250°C.